Secoidaby batteet



(No Modl) v l n r l 7 sheets-Sheen 1; M. P. LAURENT-GELY 3i TJMS, l SEGONDARYBATTERY.

No. 446,527. Patented feb. l?, MEQL Flori fawn@ M' M WW @Y uw man.) A 7 sheets-sheen 2. A. M, E', LAURENTELY n' A. TIMVH SBGONBRY BATTERY. No. L/?. Ptente; ebllfl:

fm@ Model.) 7 sheetssheet 3. LLM; E. LAURENT-CELS( 8L A. TIMMS.

SECONDARY BATTERY.

No? A16,527. Patented Feb, 17,18%

v 7 sheets-sheen 5. M. F. LURENT-CELY 85 A. TMMS.

(No Model.)

SECONDARY BATTERY.

Patented Peb. 17,1891.`

7 Sheets-Sheet A. M. I'. LAURENT-CELS( 8v A. TIB/INES.

(No Model.)

SECONDARY BATTERY.

Patented Feb. 17,13%

IUI@ 4 @DDU UGO@ (N6 Model.)

7 Shmets--Sheei` 'i'.l A. E'. LAURENT-GE-LY -ll: A. HW.:

SBGNDARY BATTERY..

No. 446,527. l mme@ Fab. 17, 11891El 5v Provence, Paris, :Tus TIMMIS, civitengiueer,

' we add as much as 45 to exclude the air as much as 5? itfersntieien I.; 4,tics torta-ll to thebottoinjand so that thefused An'rnuavimutu Fenner-)1s LAUREN A, TmtifnsjoFtoNDoN, ENGLAND; y

"escono/tav BATTERY.

l 'sPncmcATIoNrqmn-ig par; gf Letter Patent. Ne. 446,527, dem; February 117,3 reel.

@theremateriale@ eel r. 347,111. aman To alll wiz/071151125 mag/concern;

Be it lmou-'n that we, ARTHUR MARIE ERAN- oIs LAURnNT-CLL'chemist, a citizen of the Republic ,of France, residing Iat 59v Rue de a' subject ot the Queen of ,Great a Brum n: George Street,

Westminster, lfondon, S. W.,

' ,y England,-h`ave invented certain newaudus`exo ,fnl Iniproxementsin and Relating toand in thelllanufacture of Electric Secondary Cells;

a fulhclear, `audexact description of the invention, reference being had to' thevaceompa- '15 nying drawings, which formpart of .thisspeci-- ficatlon. 4 .l The objects of ourinventionare to produce electrical plates for use insecoudary batteries'-f.,.e., positive (oranode) audlnegative- :o (or cathode) plates-which have much lessy density and much more storage capacity than any previously made or described;

'lhe density of onranodes (cellular peroxide of lead) is only 4.5 to tive as against a density 25 of seven to nine in the best previously-de!4 scribed plates of ordinary peroxide of lead,

r 4'while the density'of lour cathodes (cellular` llead) is only three to 3.5.as against a-density of six toeight inspongy lead. Again, we are 3o able to store'thirty-five to forty ampere-hours per kilo of active material'in ourcellsas. against twenty-live to twenty-eight amperehours in the best previousl i made orde- 'scribed cells, and the rate of charg'. and dis- 3 5 charge which we employ is nearly double that used heretofore. 4

In the manufacture ofthe above plates, anodes, and cathodes- We' .use the following' `means andprocesses. y j 1 V Wefmeltchloride of lead, (which any one can do,as this is' common property),.apd then twenty-five per..cent. of The heat inl the furnace preference a closed fone, so as possible) we pro-.fer to have as' ,high was i550 centigrade.

pure metallic zinc.

(which is by l,Thisis a most'important','featnrl The fused .mixture is. then run ,inioji-areeeiyer, and We find 1t lan important featu'revto make. lthis reilly rvlarge.-. toex'1able the impuri- Erance, .andILLIS AIIGUS?V resid-ing at Great i .h ldsv the molten. mixture is either linedy with or more than vone p'iece, and we find it'convenient to run some ordinary lead, whichv protects the bottom of the. receiver from the at- .hea-vierthan the mixture. The mixture is after'descrihed, and cast into anyrequired takenffromy `the molds and are treated as follows, after being` washed in a coldl concentrated .solution of hydrochloric acid. The washingof the pastiles in concentrated hydrochloric acid is-effccted to destroy any metallic oxides-which maybel in the pastiles,

as .withoutzths in the, course'of formingA the, 'platesthe sulpb uric acid used causes soluble sulphatcs to be formed and the pastilesdisintebody forms a store of heat. ,The vessel which then poured into suitable molds, as herein- 'ornade in one ypiece ofrefractor'y material.

,tacks of the fus'ed body. Metallic lead is t form s.' 'The pas'tiles (orother forms) are then f and We do hereby declare the following to be.,-

grate; but we would have it very distinctly ,understood (as it is one ofthe main features in our invention) that byxour process We do not make andalmos't entirely prevent the making of metallic oxide, and', further, by, way of explana'tiomchlorideof lead eontainsnol'lydrate;

but chloride 9i zincdoes contain hydrate, and consequentlya fused mixture which contains the two chlorides'of lead, and zinc contains chloride of lead, chloride o'f zinc, oxide of lead, and oxide of zinc,`and' this mixture or lcombi- 'nationwhen treated by sul'phnrie acid causes theformationot sulphate of lead, 'and more especially sulphate of zine, which are most destructible to the plates.` On the other hand,

if metallic-zinc,

which4 contains no hydrate, is mixed with fused or melted chlorideof-'lead a pure compound of chloride of lead and chloride of zinc is obtainedwhich is clear oi. the oxides ofl these metals., This is a most' inaportant and quite newinventiom The negative pastilcs are then washedi purewater and afterward dried. (We nd 120O centigrade a convenient heat.) They are then lplaced in molds and spaced, and when the molds are closed, pure lead, with tive per cent. to seven per cent. antirnouy, is run in and forms a frameworkjand also a tang, which is used as hereinafterdcscribed; The heat requisite toV about 3509:

centigrade) is considerably less TIO(r I melt the antimonjcus lead (say l l @Asser tlie solution being pure cold unter with u lcwdrops ot hydrochloric' e'eld. liiisv operai-ion cette -s when lient to be given oil? and when the active materiel is sott and perfect. lt vis now cellular leed witlrn density ottlirce to ,3.5. l lie plntes are then washed in pure cold writer.

The positive pnetiles are placed ou zinc y in pure unid unter, with. o. little hydrociiiorie scid, till they ure thoroughly transformed into metallic cellular leed, and are tiren washed in cold witter. They are then l'lented nt' e moderate lient in Contact with oir, 'which is iucreesed up to 300 centigrede, when tite pasillos' 1eccome cellular litliurge, Witli'n. density ot tive, which, is elocut one-heli the 1density of any oliier'fretive meteriztl.

We do not use any het 'noter or liot solutions or nu electric current to produce the pristilos of cellular leed end cellular lithergc.

The fusion und reduction of chloride of leed not nerr, but is common property; but the' nddition ot metallic zinc is new, nud the conend cnet 'round them, 'above described.`

'.llie und plates nrenow pntiulend-lined 4 or enrtlienwere, gloss, or other suitable boxes end'cougiled up und clisirged witheu electric current ot' two ampres `per kilo of leed plates. This is about double the amount used before lieve is quiteneiv. Thelced tung allows n rod to be placed in o slot from below und any` one or more plates to be removed. A rod is threaded und luis nuts ou it (und Washers, preferably) to make goed contacts.

We do not bind ourselves to the exact in'- gredients named,lout to them or their known equivalent.

The drnwings herewith, coupled with the following description, will ineke our invention to be more rendily understood.

ln the accompanying drawings, Figures .l und 2 are respectively scrosssection und 1ongitudin'nl section of 'the furnace-for melting tige mixture ot chloride of leed'end metallic 'eine Figs. 3, fl, und 5 are respectively en end View. c longitudinulelevntion, and a plan of Afirst under the 'cest-iron sequent Aformation' oi" a mixture free from lxy for chersing in the the positive postiles is end metallic zinc.

this. The vsrrengement of coupling we be-v nmold vfor casting the postile's. Figs. G und? nrc respectively o vertical section and e, plnn of e. vet for washing the pestiles in concentrated hydrochloric acid. Figs. S end 9 are respectively n vertical section und n plan of e vet for thc chemical treetmentlof the pastiies which are to be turned into cellular leed to form the positivoplntes. Figs. l-O and ll nre respectively nu cud View and en external elevation of the frames which we employ to cast e frame-work of untimonious leed around the pnstiles. Fig. 12 Fig. ll. Fig. 13 is un elevation of one-half ot this treme and showsthe internal face thereof. Fig. 1l is o plain view of the frame. Figs. l5, 16, and 17 ero respectively en end view, e plan, and another end View of the templet used' for securing;` in the frame e proper spacing around and between the pestiles whichlieve to be connected together by a framework of antimonlous lead so as to form .an accumulator-plate. Figs. 1S and 19, ay b c d efghz'jkl m n o p, show the various forms according to which the pestiies ere cast. 'lhe melting-furnace, procticelly a closed one, (shown in transverse section in. Fig. l und in longitudinal section iu Fig 2,)'consists ot o furnace having several stories A A ot a cusbiron pan B, provided with.' sole or ting' stones ot refractory materiel. This pun is covered with removable flog-stones C,on the top of which we place' cast-iron plates D,form ing a. flue. -Theiliot gases ot' combustion poss pen und then into the flue C D Without everpommunicnting with the inside of the furnace.' After leaving liuc C D they enter the chimney E..

There are three doors arranged 'on the outside of the melting-furnace. The first F is mixture of chloride of leed It has au extension formed oy e deed-plete G, under which the hot gases of combustion Vpass in the beginning ot the operation. The chloride of lead fuses on this deed-pletennd falls then into the pen.y The 'metallic zinc is then added and the mixture is removed by menus of a. cust-iron ladle in troduced through the second door H, celledi costing-door. `We may usethe equivalent of metallic zinc. A third doorl or stirringup door is used to stir up the mixture While it is `intl1e molten state. At each of these issues there are uli-ranged lines J `l',wlrich'col lect the fumes orvepors. These fines unite into s, single one of conical shape yo ning into e condensation-chamber. Under t e pen there is a. flogging K of refractory bricks, in.- clined on. both sides, so es to form channels in the vmiddle for the purpose of collecting, the molten mixture in cese of ,accident und preventing it felling into the fire. It is very desirsolefor the reasons hereinat ter appesi'- iug, to esclude nir es much es possible from the mixture, und the ebove form of furnace enables this to be done more com pletelythan v@my other.

After having teken some ot thc molten is .n vertical cross-section of mixture by means ofthe cast-iron ladle itis run'into a hinged cast-iron -mold A', Figs. 3,

4 and-5, provided internally with cells V Y 'their lower part with a of anyshape.4 permit of any required form being given to' the pastiles. lVe show a b cd, the., a series of pastiles of lvaried forms.v The next stage consists in washing the pastiles in concentrated hydrochloric acid. Although we effect fusion in a closed vessel, itis impossible to' entrance of air through the entirely avoid the furnace-door, and consequently to prevent the formation of oxychlorides in a small legree. The zincl and leadoxideswhleh are formed 1n ust thereforebbe eliminated.- 'To ef' feet this We arrange the pastiles, Figs. 6 and 7, on leaden trays A24/l2 A2, provided with holes, permitting easy circulation ofthe liquid,

-and with projections ai a2 a2, so' as to leave In this acid anyoxides are transformed into of lead.

'of the stone tap and a circulation of water established for all turned' into cellular lead.

' Figs. 8 and up with Water, in which the chlorides, and the operation is continued until the pastlles contain nothing but pure chloride The vat is then emptied by means the purpose of vremoving the excess of hydrochloric-acid retained by the plates.

The tvro aforesaid operations apply equally to the pastiles which are to form the positive plates and to lthose .used in the manufacture of the negative' plates. After the second operation the past-iles are divided and the negativebnes. -Each goes a different treatment.'

First, `with respect to the positive pastiles, by means of reduction andvv transformation into lithargc. -The positive pastiles,'jcleaned and Washed, as has been explained above, are subjected to a reduction process to'be first of This reduction is effected by an electro-chemicalmethod, 9, by means of zinc plates d3 d, separat-ed by lead blocks e eq and piled up in a vat D3, lined with lead. 'lhis vat is lled chloride of zinc resulting from the electrochemical action is dissolved. It vis provided with a stoneware grou p undertap, or of r'any other material not alfected bychemicals. for the purpose of emptying the liquid. After the reduction has been Aeffected in these conditions the positive pastiles are deprived of all the chlorine which enteredinto their previous composition. There remains now nothing but pure cellular lead. The pastiles are then taken into a stove heated to a temperature ranging between 250 and 300 centi` Fahrenheit.) Under'- grade, (say 489 to 570 a' yis ,the hinge. Cells -r vided with a hollow E4 E4, tothe projection with which the frame of a'ninto two grou ps-the positive pastiles ous lead is run thlfohg'h the opening L4.

. of pure' cellular formation into cellular litharge is effected.

vol

round .the negative one of chloride-oii lead' not yet reduced by the sainemeans and with' .the saine mold, as we are now going'to deV Scribe. It consists, essentially, Figs. l() to '17,'

of two cast-i ron frames AiAjointed together by means olla hinge lll. 1 It can swing round 'a segment@4 by means of trnnnions D4. Each hollow frame is all around and .internally prowhieh correspond timonious lead must be provided. It is, be'- sides, lined with asbest-us mill-boardof a'thick-l ness suicient to form a slightly-elastic surface.' A platen Fo'fcast-iron keeps this asbestus mill-board in position 'and permits of any degree of pressure being imparted by by means of the -nu'ts fifi. The pressureon the two -platensis obtained by means off 'six cam-levers G4.

To 'cast a frame the yme'ldis y placed horizoutally'and opened at 'right angles. Atemplet 114, which is an exact counterpart of the spacesleftbetween and allaround the pastiles,islaid on the lower platen, Figs. l5,

16, and 1 7. It is provided Withfour prcjecg tions z"l i", which enter holes'Jr4 J4. in the platenv and serve to insnrefthe exact position. ozf the 'pastilea v The pastiles are placed in theopen parts of. the templet, so that spaces of uniformsize are therefore left between 'the pastiles.:

-The tem-piet i/sxremoved by means of handles' K4 without disturbing the pastil'es. The npper platen is lowered andA the tightening cani levers are operated, The pastiles are thus pressed between the pieces of asbestus mill-- board and cannot be shifted. The mold being then brought intoavertical position,antimonif The molten metalV fills .up the spaces left between the pastiles and around the platens. The pastiles are therefore connected firmly by means of a framework ofA lead. brought back into its hori opened, theframework is withdrawn,- and it is sufficient to let the leaders M* M4 drop to obtain the accumulator-plate.

Secondly, "with respect tot-he negative pasf tiles. These are now provided witha framei .The mold, being Work of antimonious lead, andthen it re. 'mains only to' reduce them int'o cellular lea'd.

These plates being still in the state of chloride Vof lead, their reduction is eieeted in the-same manner as in thecaseof the positive platee# l, that is, byA means of an edcetrolytic4 bathijn, al vat containing the plates y.to be redncind zinc plates.-

zontal position, is

Finally, `we have thus obtainedpositive plates lconsisting ot' pastiles of,cellularlth` ange, and on. the other hand negative lplates lead', the pastiles 'n eitherA kindof plate being strongly connected with one :mother by means of a frame-work of an t'iulouious lezul. 'lhere remains oulyio group bolli kinds of plateaso es to form them elecn tricall y by the-ordinary means.

llawing new particularly {lescrihed and asveriaiued ihe nature of our said invention, .we declare that what we claim ie-P l.` 'lhc process of forming material for soeomlary-battery plates, consisting in lfusing or meltinggeliloride of. lead, adding metallic zinc l`therein, andsubseqliently running the mass into alargue receiver-lane allowingthe impurilies of lthe mixt-uizeto fall lo the bottom of receiver, substantially as specified..

for secondary batteries, consisting inV fusing or inciting chloride oi" lead, adding meiallie' zinc to said chloride el' lead, formingthe m ass Y in suitable molds, and :subsequently washing 4the formed .plates iu concentraed hydrochloric acid, substantially speeiiied.

The process el forming poeitive platesfor secondary batteries, consisting in irst fueing or melting chloride of lead und metallic zinc, then formingthe samein suitable molds, then washing the formed plaies' in coneen trated hydrochloric acid, theereducing the plates tolithargo, and then forming :iframe- 'worlvof autimouious lead around like plaies, subsiantially as spccilierl.

4. The process of forming negalive plates l for secondary batteries, consisting; in first fueing or melting chloride of lead, their adding metallic zine Lhereto,.theu forming; the same in suable molds, then washing Vthe formed -plelesin concentrated hydrochloric acid, then formingafname-work of antimouious lead around the plates, and subsequently reduc ing the plates o cellular lead, substantially as specified.

"5. The process of forming plates for scc- 2. 'The'4 process of forming :positive plates millar-y batteries, eousieling iu fusing or mell- -iug chloride of lead. ami metallic zine, peliring the mass into a receiver lined wirlr or made of a refractory material faced with a proteeing stratum oi' ordinary lead, end sui sequeutlypom'ing the mixture in'o suiable mold and washiuar the material thus formed ixilconcentrated hydrochloric acid, substantially as specieli. u

6., rlhe process oi forming; paies for seeondary batteries, consietingri in fusing er meileiing chloride o?- ieed and metallic ziiie, then 'forming 'said masia' iui'o plaies, and subsevquenil'ycoupling theplates in seis liedje.

Mls, claim the foregoing, in eoejimeiori Willi the said ARTHUR liners llmirzol's. Lf oi-.mier CLY, l have hereunto sei my han@ iiis lili?. day of lliarei'l, 'liflO l. A, fillilllirl'lf. W imiesses te 'he signature ot' l. A.. Timmie:

FlmDER'eK l@morren ijewixeog' l 'lei-', Ili'orleg/ Avenue,'irfoofl Grec/.11,llou-liolz. EDWARD GUs'rave/.lnehme @oemig lrlfs'man, 733 lynmimmi Rrr/lc?, Sol/ill foifen 71am', f 

